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TWI796400B - Powder composition for forming thick film conductor and paste for forming thick film conductor - Google Patents

Powder composition for forming thick film conductor and paste for forming thick film conductor Download PDF

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TWI796400B
TWI796400B TW107144766A TW107144766A TWI796400B TW I796400 B TWI796400 B TW I796400B TW 107144766 A TW107144766 A TW 107144766A TW 107144766 A TW107144766 A TW 107144766A TW I796400 B TWI796400 B TW I796400B
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powder
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TW201927927A (en
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粟窪慎吾
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日商住友金屬鑛山股份有限公司
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Abstract

本發明提供可形成容易施以鍍敷之厚膜導體之厚膜導體形成用粉末組成物及厚膜導體形成用糊料。 本發明之厚膜導體形成用粉末組成物包含導電粉末、無鉛玻璃粉末及氧化錳粉末,前述玻璃粉末含量,相對於前述導電粉末100質量份,為1.5質量份以上5質量份以下,前述氧化錳粉末含量,相對於前述導電粉末100質量份,為0.5質量份以上3.5質量份以下。The present invention provides a powder composition for forming a thick-film conductor and a paste for forming a thick-film conductor capable of forming a thick-film conductor that can be easily plated. The powder composition for forming a thick-film conductor of the present invention includes conductive powder, lead-free glass powder, and manganese oxide powder. The powder content is not less than 0.5 parts by mass and not more than 3.5 parts by mass with respect to 100 parts by mass of the aforementioned conductive powder.

Description

厚膜導體形成用粉末組成物及厚膜導體形成用糊料Powder composition for forming thick film conductor and paste for forming thick film conductor

本發明係關於厚膜導體形成用粉末組成物及厚膜導體形成用糊料,更詳言之,係有關於製造晶片電阻器、電阻網路及混成IC等時,用以於陶瓷基板上形成厚膜導體而使用之厚膜導體形成用粉末組成物及厚膜導體形成用糊料,尤其有關無鉛厚膜導體形成用粉末組成物及厚膜導體形成用糊料。The present invention relates to a powder composition for forming a thick-film conductor and a paste for forming a thick-film conductor. Thick-film conductor-forming powder composition and thick-film conductor-forming paste used for thick-film conductors, especially lead-free thick-film conductor-forming powder composition and thick-film conductor-forming paste.

使用厚膜技術形成厚膜導體時,一般將導電率高的導電粉末與玻璃粉末等之氧化物粉末一起分散於有機載劑中,獲得厚膜導體形成用糊料。接著,進行將該糊料使用網版印刷法於氧化鋁等之陶瓷基板上塗佈成特定形狀,於500℃以上900℃以下燒成而形成厚膜導體。When using thick-film technology to form thick-film conductors, generally high-conductivity conductive powder and oxide powder such as glass powder are dispersed in an organic vehicle to obtain a paste for thick-film conductor formation. Next, the paste is coated in a specific shape on a ceramic substrate such as alumina by screen printing, and fired at 500°C to 900°C to form a thick film conductor.

作為導電粉末係使用可在氮氣環境中燒成之導電率高的Au、Ag、Pd及Pt等之數平均粒徑10μm以下之粉末,該等中,主要使用便宜之Ag粉末及Pd粉末。As the conductive powder, Au, Ag, Pd, and Pt with high conductivity that can be fired in a nitrogen atmosphere are used, and the number average particle diameter is 10 μm or less. Among them, cheap Ag powder and Pd powder are mainly used.

作為玻璃粉末,係使用軟化點容易控制且化學耐久性高的硼矽酸鉛粉末或鋁酸硼矽酸鉛系玻璃粉末。然而,近幾年來,基於防止環境汙染之觀點,對於不含鉛的導體糊料的要求日益提高,故作為玻璃粉末,要求其替代材料。因此專利文獻1中揭示無鉛之厚膜導體形成用組成物。As the glass powder, lead borosilicate powder or lead aluminate borosilicate-based glass powder whose softening point is easy to control and has high chemical durability is used. However, in recent years, from the viewpoint of preventing environmental pollution, there has been an increasing demand for a lead-free conductor paste, and therefore, an alternative material has been demanded as a glass powder. Therefore, Patent Document 1 discloses a lead-free thick-film conductor-forming composition.

不過,使用此等厚膜導體形成用組成物形成之厚膜導體適合使用作為電子工業所用之晶片電阻器、電阻網路、混成IC等之電子零件之電極等。例如,如圖1之剖面示意圖所示,晶片電阻器100具備氧化鋁基板10、藉由厚膜導體形成之由上面電極21與側面電極22與背面電極23所成之內部電極20、由氧化釕系厚膜等所成之電阻膜30、及覆蓋電阻之絕緣玻璃的保護膜40。且,內部電極20之露出電極面上,為了提高焊料性,藉由電解鍍敷進而分別形成由Ni鍍層等所成之中間電極50與由Sn-Pb焊料鍍層或代替其之Sn系合金之無鉛焊料鍍層等所成之外部電極60。 [先前技術文獻] [專利文獻]However, thick-film conductors formed using these thick-film conductor-forming compositions are suitable for use as electrodes of electronic components such as chip resistors, resistor networks, and hybrid ICs used in the electronics industry. For example, as shown in the schematic cross-sectional view of FIG. 1 , a chip resistor 100 includes an aluminum oxide substrate 10, an internal electrode 20 formed of a top electrode 21, a side electrode 22, and a back electrode 23 formed of a thick film conductor, and an internal electrode 20 made of ruthenium oxide. Resistor film 30 made of thick film etc., and protective film 40 of insulating glass covering the resistor. Also, on the exposed electrode surface of the internal electrode 20, in order to improve the solderability, the intermediate electrode 50 made of Ni plating, etc. and the lead-free lead-free layer of Sn-Pb solder plating or a Sn-based alloy instead of it are respectively formed by electrolytic plating. External electrodes 60 made of solder plating or the like. [Prior Art Document] [Patent Document]

[專利文獻1] 日本特開2012-043622號公報[Patent Document 1] Japanese Patent Laid-Open No. 2012-043622

[發明欲解決之課題][Problem to be solved by the invention]

厚膜導體形成用組成物中,為了確保厚膜導體與氧化鋁基板等之陶瓷基板之密著性,而含有玻璃粉末。然而,玻璃粉末之含量多時,有對厚膜導體不易施以鍍敷之問題。The composition for forming a thick-film conductor contains glass powder in order to ensure the adhesion between the thick-film conductor and a ceramic substrate such as an alumina substrate. However, when the content of the glass powder is large, there is a problem that it is difficult to apply plating to a thick-film conductor.

本發明係鑒於此等情況,而可形成容易施以鍍敷之厚膜導體。目的在於提供厚膜導體形成用粉末組成物及厚膜導體形成用糊料。 [用以解決課題之手段]In view of these circumstances, the present invention can form a thick-film conductor that can be easily plated. The object is to provide a powder composition for forming a thick-film conductor and a paste for forming a thick-film conductor. [Means to solve the problem]

為了解決上述課題,本發明之厚膜導體形成用粉末組成物係包含如下之厚膜導體形成用粉末組成物:導電粉末、無鉛玻璃粉末、及氧化錳粉末,前述玻璃粉末含量,相對於前述導電粉末100質量份,為1.5質量份以上5質量份以下,前述氧化錳粉末含量,相對於前述導電粉末100質量份,為0.5質量份以上3.5質量份以下。In order to solve the above-mentioned problems, the powder composition for forming a thick-film conductor of the present invention includes the following powder composition for forming a thick-film conductor: conductive powder, lead-free glass powder, and manganese oxide powder. 100 parts by mass of the powder is not less than 1.5 parts by mass and not more than 5 parts by mass, and the content of the manganese oxide powder is not less than 0.5 parts by mass and not more than 3.5 parts by mass relative to 100 parts by mass of the conductive powder.

前述氧化錳粉末可為Mn3 O4 粉末。The aforementioned manganese oxide powder may be Mn 3 O 4 powder.

前述導電粉末可選自銀粉末、鈀粉末及鉑粉末中之至少一種。The aforementioned conductive powder can be selected from at least one of silver powder, palladium powder and platinum powder.

前述玻璃粉末之玻璃轉移溫度可為400℃以上600℃以下,軟化點為500℃以上700℃以下。The glass transition temperature of the aforementioned glass powder may be 400°C to 600°C, and the softening point is 500°C to 700°C.

前述玻璃粉末可包含鉍。The aforementioned glass powder may contain bismuth.

又,為了解決上述課題,本發明之厚膜導體形成用糊料係包含前述厚膜導體形成用粉末組成物、溶劑與樹脂之混合物的厚膜導體形成用糊料。Furthermore, in order to solve the above-mentioned problems, the paste for forming a thick-film conductor of the present invention is a paste for forming a thick-film conductor comprising a mixture of the aforementioned powder composition for forming a thick-film conductor, a solvent, and a resin.

又,為了解決上述課題,本發明之厚膜導體形成用糊料係包含如下之厚膜導體形成用糊料:導電粒子、無鉛玻璃粒子、氧化錳粒子、溶劑、及樹脂,前述玻璃粒子含量,相對於前述導電粒子100質量份,為1.5質量份以上5質量份以下,前述氧化錳粒子含量,相對於前述導電粒子100質量份,為0.5質量份以上3.5質量份以下。 [發明效果]Also, in order to solve the above-mentioned problems, the paste for forming a thick-film conductor of the present invention includes the following paste for forming a thick-film conductor: conductive particles, lead-free glass particles, manganese oxide particles, solvent, and resin, the content of the aforementioned glass particles, The content of the manganese oxide particles is 0.5 to 3.5 parts by mass relative to 100 parts by mass of the conductive particles. [Invention effect]

依據本發明之厚膜導體形成用粉末組成物及厚膜導體形成用糊料,可獲得容易施以鍍敷之厚膜導體。According to the powder composition for forming a thick-film conductor and the paste for forming a thick-film conductor of the present invention, a thick-film conductor that can be easily plated can be obtained.

以下,針對本發明之具體實施形態詳細說明。又,本發明並非限定於以下實施形態,在不變更本發明要旨之範圍內可適當變更。Hereinafter, specific embodiments of the present invention will be described in detail. In addition, this invention is not limited to the following embodiment, In the range which does not change the summary of this invention, it can change suitably.

本發明之厚膜導體形成用粉末組成物包含導電粉末、無鉛玻璃粉末及氧化錳粉末。該組成物中,前述無鉛玻璃粉末含量,相對於前述導電粉末100質量份,為1.5質量份以上5質量份以下,前述氧化錳粉末含量,相對於前述導電粉末100質量份,為0.5質量份以上3.5質量份以下。依據此厚膜導體形成用粉末組成物,如以下所說明,藉由燒成易施以鍍敷之玻璃而熔融,而可抑制浮出於厚膜導體表面之現象,可獲得施以鍍敷優異之厚膜導體。The powder composition for forming thick-film conductors of the present invention includes conductive powder, lead-free glass powder and manganese oxide powder. In this composition, the content of the lead-free glass powder is 1.5 to 5 parts by mass with respect to 100 parts by mass of the conductive powder, and the content of the manganese oxide powder is 0.5 parts by mass or more with respect to 100 parts by mass of the conductive powder. 3.5 parts by mass or less. According to this powder composition for forming thick-film conductors, as described below, by firing and melting glass that is easy to apply plating, the phenomenon of floating on the surface of thick-film conductors can be suppressed, and excellent plating can be obtained. thick film conductors.

本發明人等,為了改善厚膜導體之施以鍍敷性,對浮出於厚膜導體表面的玻璃重複積極研究之結果,發現藉由於厚膜導體形成用組成物中添加氧化錳粉末,可抑制於燒成所得之厚膜導體表面浮出之玻璃。進而意外的是藉由添加氧化錳,可於厚膜導體表面形成微細階差之條紋花樣。而且,由於於厚膜導體表面析出微細階差之花樣,故可期待厚膜導體表面與Ni鍍敷膜等之密著性因錨定效果而提高。亦即藉由玻璃浮起抑制與錨定效果,而使厚膜導體與鍍敷膜之密著性更良好。The inventors of the present invention, in order to improve the plating property of thick-film conductors, as a result of repeated active research on glass floating on the surface of thick-film conductors, found that by adding manganese oxide powder to the composition for forming thick-film conductors, A glass that suppresses floating on the surface of thick-film conductors obtained by firing. Furthermore, it is surprising that by adding manganese oxide, a striped pattern with fine steps can be formed on the surface of the thick film conductor. Furthermore, since fine step patterns are deposited on the surface of the thick-film conductor, it is expected that the adhesion between the surface of the thick-film conductor and the Ni plating film and the like will be improved by the anchoring effect. That is to say, the adhesion between the thick-film conductor and the plating film is better through the glass floating suppression and anchoring effects.

本發明係基於此等見解而完成者。以下針對本發明,以(1)厚膜導體形成用粉末組成物及(2)厚膜導體形成用糊料之順序詳細說明。又,亦針對(3)使用本發明之厚膜形成用糊料之厚膜導體之製造方法及(4)厚膜導體分別詳細說明。This invention is completed based on these knowledge. Hereinafter, the present invention will be described in detail in the order of (1) the powder composition for thick-film conductor formation and (2) the paste for thick-film conductor formation. In addition, (3) a method for producing a thick-film conductor using the thick-film-forming paste of the present invention and (4) a thick-film conductor are also described in detail.

[(1)厚膜導體形成用粉末組成物]   本發明可成為無鉛之厚膜導體形成用粉末組成物,該組成物可至少由導電粉末及氧化物粉末構成。此處,所謂無鉛意指於不包含鉛時,容許起因於例如含鉛之導電粉末或氧化物粉末等之原料粉末或製造過程中混入鉛而作為不可避免雜質之鉛包含100質量ppm以下之情況。[(1) Thick-film conductor-forming powder composition] The present invention can be a lead-free thick-film conductor-forming powder composition, and the composition can be composed of at least conductive powder and oxide powder. Here, the so-called lead-free means that when lead is not contained, it is allowed to contain lead as an unavoidable impurity at a rate of 100 mass ppm or less due to the inclusion of lead in the raw material powder or the manufacturing process such as lead-containing conductive powder or oxide powder. .

(導電粉末)   本發明所用之導電粉末宜為通常之厚膜導體形成所用者,舉例為例如Au、Ag、Pd、Pt等之貴金屬。該等貴金屬之粉末可使用1種或組成2種以上使用。其中,基於熔點低或成本之觀點,較好使用Ag粉末、Pd粉末或該等之混合粉末。(Conductive powder) The conductive powder used in the present invention is preferably used for forming thick-film conductors, such as noble metals such as Au, Ag, Pd, and Pt. These noble metal powders can be used alone or in combination of two or more. Among these, it is preferable to use Ag powder, Pd powder, or a mixed powder thereof from the viewpoint of low melting point or cost.

導電粉末之數平均粒徑較好為10μm以下,基於本發明之厚膜導體形成用糊料之塗佈性惡化之觀點,更好為0.1μm以上5.0μm以下。數平均粒徑超過10μm時,有升溫過程之燒成變慢之情況,而欠佳。例如使用Ag粉末與Pd粉末之混合粉末時,基於本發明之厚膜導體形成用糊料之塗佈性惡化之觀點或Ag粉末與Pd粉末之均質分散之觀點,較好將Ag粉末之數平均粒徑設為0.1μm以上3.0μm以下,Pd粉末之數平均粒徑設為0.01μm以上0.3μm以下。此處,數平均粒徑係自粉末的掃描顯微鏡照片(SEM像)求出之數平均粒徑。又,導電粉末之形狀有粒狀、片狀等,但對於使用何種形狀者,係對應於其用途適當選擇。The number average particle diameter of the conductive powder is preferably at most 10 μm, more preferably at least 0.1 μm and at most 5.0 μm, from the viewpoint of poor coatability of the thick-film conductor-forming paste of the present invention. When the number average particle diameter exceeds 10 μm, the firing in the heating process may slow down, which is not preferable. For example, when using a mixed powder of Ag powder and Pd powder, it is preferable to average the number of Ag powders from the viewpoint of deterioration of the applicability of the thick-film conductor-forming paste of the present invention or the homogeneous dispersion of Ag powder and Pd powder. The particle diameter is 0.1 μm to 3.0 μm, and the number average particle diameter of the Pd powder is 0.01 μm to 0.3 μm. Here, the number average particle diameter is the number average particle diameter calculated|required from the scanning micrograph (SEM image) of a powder. Also, the shape of the conductive powder is granular, flake, etc., but which shape to use is appropriately selected according to the use.

(無鉛玻璃粉末)   本發明中,作為無鉛玻璃粉末,可使用SiO2 -B2 O3 -鹼土類氧化物系玻璃粉末、或Bi2 O3 -SiO2 -B2 O3 系玻璃粉末或ZnO-SiO2 -B2 O3 系玻璃粉末等之玻璃粉末。考慮用以作成厚膜導體之燒成溫度,該等玻璃粉末之玻璃轉移點期望為400℃以上600℃以下,軟化點為500℃以上700℃以下。作為所用之無鉛玻璃,可為結晶化玻璃,意可為未結晶化之玻璃。又,無鉛玻璃粉末係不含鉛之玻璃,或者為作為不可避免雜質的鉛含100質量ppm以下之玻璃粉末。此處,玻璃轉移點係於大氣中以熱機械分析法(TMA)測定使玻璃粉末再熔融所得之桿狀試料,作為顯示熱膨脹曲線之轉折點的溫度而測定。且,軟化點係以示差熱分析法(TG-DTA)於大氣中測定玻璃粉末,比展現最低溫側之示差熱曲線減少的溫度更於高溫側之下一示差熱曲線所減少之峰值溫度。(Lead-free glass powder) In the present invention, SiO 2 -B 2 O 3 -alkaline earth oxide glass powder, Bi 2 O 3 -SiO 2 -B 2 O 3 glass powder or ZnO glass powder can be used as the lead-free glass powder. - Glass powder such as SiO 2 -B 2 O 3 -based glass powder. Considering the firing temperature used to make thick-film conductors, the glass transition point of these glass powders is expected to be 400°C to 600°C, and the softening point to be 500°C to 700°C. The lead-free glass used may be crystallized glass, meaning uncrystallized glass. In addition, the lead-free glass powder is a glass that does not contain lead, or a glass powder that contains 100 mass ppm or less of lead as an unavoidable impurity. Here, the glass transition point is measured as a temperature showing an inflection point of a thermal expansion curve by measuring a rod-shaped sample obtained by remelting glass powder by thermomechanical analysis (TMA) in the air. In addition, the softening point is measured by differential thermal analysis (TG-DTA) in the atmosphere of glass powder, and the temperature of the differential thermal curve showing the lowest temperature side decreases more than the peak temperature of the differential thermal curve below the high temperature side.

作為無鉛玻璃粉末,藉由含有鉍,而獲得提高藉由厚膜導體形成之內部電極與氧化鋁基板等之陶瓷基板的接著強度之效果。例如,無鉛玻璃粉末中之鉍含量藉由將作為Bi2 O3 設為30質量%以上70質量%以下,而可獲得接著強度之提高效果。By containing bismuth as the lead-free glass powder, the effect of improving the bonding strength between internal electrodes formed of thick-film conductors and ceramic substrates such as alumina substrates is obtained. For example, by setting the content of bismuth in the lead-free glass powder to 30% by mass or more and 70% by mass or less as Bi 2 O 3 , an effect of improving adhesive strength can be obtained.

厚膜導體形成用粉末組成物中之無鉛玻璃粉末之含量,相對於導電粉末100質量份,設為1.5質量份以上5質量份以下,考慮與基板之接著強度或鍍敷性、焊料之濡濕性等時,更好為1.5質量份以上3質量份以下,又更好為1.5質量份以上2.7質量份以下。無鉛玻璃粉末之含量少於1.5質量份時,有與陶瓷基板之接著強度降低之虞。又,該含量多於5質量份時,有發生於厚膜導體表面浮出玻璃之現象之情況,藉此,有對於厚膜導體之鍍敷性、焊料之濡濕性等降低之虞。The content of lead-free glass powder in the powder composition for thick film conductor formation is 1.5 mass parts to 5 mass parts with respect to 100 mass parts of conductive powder, considering the adhesion strength with the substrate, plating property, and solder wettability At the same time, it is more preferably at least 1.5 parts by mass and not more than 3 parts by mass, and more preferably at least 1.5 parts by mass and not more than 2.7 parts by mass. When the content of the lead-free glass powder is less than 1.5 parts by mass, the adhesive strength with the ceramic substrate may decrease. Also, when the content is more than 5 parts by mass, the phenomenon of glass floating on the surface of the thick-film conductor may occur, thereby degrading the platability of the thick-film conductor, the wettability of the solder, and the like.

無鉛玻璃粉末中之玻璃組成,可使用可實現上述玻璃轉移點或軟化點之組成者。玻璃粉末中,SiO2 之含量較好為15質量%以上60質量%以下。SiO2 之含量少於15質量%時,有玻璃之耐藥品性降低之虞,或厚膜導體中之玻璃耐候性、耐水性及耐藥品性降低之虞,其結果,對厚膜導體進行Ni鍍敷時有發生鍍敷不良等問題之虞。另一方面,SiO2 含量多於60質量%時,玻璃之軟化點變過高,而有損害厚膜導體與陶瓷基板之密著性之情況。The glass composition in the lead-free glass powder can use a composition that can realize the above-mentioned glass transition point or softening point. In the glass powder, the content of SiO 2 is preferably from 15% by mass to 60% by mass. When the content of SiO2 is less than 15% by mass, there is a possibility that the chemical resistance of the glass may decrease, or that the weather resistance, water resistance, and chemical resistance of the glass in the thick film conductor may decrease. As a result, the thick film conductor is subjected to Ni There is a possibility that problems such as defective plating may occur during plating. On the other hand, when the SiO 2 content is more than 60% by mass, the softening point of the glass becomes too high, which may impair the adhesion between the thick-film conductor and the ceramic substrate.

關於無鉛玻璃粉末之形狀,舉例為球狀或針狀等之各種者,並未特別限定,但無鉛玻璃粉末之藉由利用雷射繞射之粒度分佈計測定之體積累積粒度分佈之D50 徑(中值徑)較好為10μm以下,基於本發明之厚膜導體形成用糊料之塗佈性等或導電粉末與無鉛玻璃之均質分散之觀點,更好為0.5μm以上3μm以下。D50 徑為10μm以上時,會阻礙導電粉末與無鉛玻璃粉末之均質分散,產生無鉛玻璃粉末之偏置,而成為使厚膜導體與基板之接著強度降低之傾向而欠佳。The shape of the lead-free glass powder is, for example, spherical or needle-like, and is not particularly limited, but the D50 diameter of the volume cumulative particle size distribution of the lead-free glass powder measured by a particle size distribution meter using laser diffraction ( Median diameter) is preferably at most 10 μm, more preferably at least 0.5 μm and at most 3 μm from the viewpoint of the coatability of the paste for forming a thick film conductor of the present invention or the homogeneous dispersion of conductive powder and lead-free glass. When the D 50 diameter is more than 10 μm, it will hinder the homogeneous dispersion of the conductive powder and the lead-free glass powder, cause the bias of the lead-free glass powder, and tend to reduce the bonding strength between the thick-film conductor and the substrate, which is not good.

(氧化錳粉末)   氧化錳粉末之含量,相對於導電粉末100質量份,設為0.5質量份以上3.5質量份以下。該含量少於0.5質量份時,有無法期待玻璃於厚膜導體表面浮出之抑制效果之虞,有無法改善鍍敷性之情況。另一方面,該含量若為3.5質量份,則可充分獲得鍍敷之改善效果,含量即使多於此,亦無法提高鍍敷性之改善效果。(Manganese Oxide Powder) The content of the manganese oxide powder is 0.5 to 3.5 parts by mass relative to 100 parts by mass of the conductive powder. When the content is less than 0.5 parts by mass, the effect of suppressing the floating of glass on the surface of the thick-film conductor may not be expected, and the platability may not be improved. On the other hand, if the content is 3.5 parts by mass, the effect of improving plating properties can be sufficiently obtained, but even if the content is more than this, the effect of improving plating properties cannot be enhanced.

針對厚膜導體之鍍敷性進行探討。於厚膜導體表面浮出玻璃時,對於厚膜導體表面之Ni鍍敷等之鍍敷性變差。於厚膜導體表面之Ni鍍敷或Sn合金系鍍敷之實施性差,於該等鍍敷面有針孔等之孔洞時,厚膜導體之Ag因大氣中之硫成分而硫化,而有電子零件之連接變不良之虞。Discuss the plating properties of thick film conductors. When the glass is floated on the surface of the thick-film conductor, the plating properties such as Ni plating on the surface of the thick-film conductor deteriorate. The implementation of Ni plating or Sn alloy plating on the surface of thick film conductors is poor. When there are holes such as pinholes on the plating surface, the Ag of the thick film conductor will be vulcanized due to the sulfur content in the atmosphere, and there will be electrons. The connection of parts may become bad.

不過,若對無鉛玻璃與不可避免地含有鉛作為構成成分之玻璃,於溫度上升之過程中的熔融性進行檢討時,兩者於同樣之軟化點,無鉛玻璃者之熔融溫度處於高溫側。於用以獲得厚膜導體之燒成過程中,以於升溫中與於一定時間之峰值溫度保持中可獲得玻璃熔融狀態之限制時間,進行氧化鋁基板等之陶瓷基板與玻璃之熔著,而確保厚膜導體之密著性。由於無鉛玻璃不易熔融,於使用無鉛玻璃之厚膜導體形成用粉末組成物,為了與基板之密著性,必須使玻璃粉末含量較多。然而,相對於導電粉末100質量份的玻璃粉末含量超過1.5質量份時,有於厚膜導體表面產生玻璃浮出之情況。相對於導電粉末100質量份的玻璃粉末含量即使超過1.5質量份,玻璃含量接近於1.5質量份時,玻璃之浮出為局部,但隨著玻璃含量增加,於厚膜導體表面之玻璃浮出面積增加。因此,藉由將相對於導電粉末100質量份的氧化錳粉末含量設為0.5質量份以上3.5質量份以下,可改善厚膜導體之鍍敷性,藉由防止施以鍍敷之厚膜導體的Ag硫化等,結果可改善電子零件之連接不良。However, when examining the melting properties of lead-free glass and glass that inevitably contains lead as a constituent component in the process of temperature rise, both of them have the same softening point, and the melting temperature of lead-free glass is on the high side. In the firing process for obtaining thick-film conductors, the fusion of ceramic substrates such as alumina substrates and glass is carried out with a limited time for obtaining a glass molten state during temperature rise and peak temperature maintenance for a certain period of time, and Ensure the adhesion of thick film conductors. Since lead-free glass is not easy to melt, in the powder composition for forming a thick-film conductor using lead-free glass, it is necessary to make the glass powder content more in order to adhere to the substrate. However, when the content of the glass powder exceeds 1.5 parts by mass with respect to 100 parts by mass of the conductive powder, glass floating may occur on the surface of the thick-film conductor. Even if the glass powder content exceeds 1.5 parts by mass relative to 100 parts by mass of the conductive powder, when the glass content is close to 1.5 parts by mass, the glass floats out locally, but as the glass content increases, the glass floated out area on the surface of the thick film conductor Increase. Therefore, by making the content of the manganese oxide powder relative to 100 parts by mass of the conductive powder 0.5 parts by mass or more and 3.5 parts by mass or less, the plating properties of the thick film conductor can be improved, and by preventing the thickness of the thick film conductor to be plated Ag vulcanization, etc., can improve the poor connection of electronic parts as a result.

又,使用利用無鉛玻璃的厚膜導體形成用粉末組成物形成厚膜導體時,相對於導電粉末100質量份的氧化錳粉末含量未達0.5質量份時,雖改善與陶瓷基板之密著性,但有無法改善鍍敷性之虞。另一方面,相對於導電粉末100質量份的氧化錳粉末含量超過3.5質量份時,有與陶瓷基板之密著性降低之情況。基於該等方面,相對於導電粉末100質量份的氧化錳粉末含量期望為0.5質量份以上3質量份以下,更期望為0.5質量份以上2.5質量份以下。Also, when a thick-film conductor is formed using a thick-film conductor-forming powder composition utilizing lead-free glass, when the manganese oxide powder content is less than 0.5 parts by mass relative to 100 parts by mass of the conductive powder, the adhesion to the ceramic substrate is improved, However, there is a possibility that the plating property cannot be improved. On the other hand, when content of the manganese oxide powder exceeds 3.5 mass parts with respect to 100 mass parts of electroconductive powders, the adhesiveness with a ceramic substrate may fall. From these points, the content of the manganese oxide powder is desirably not less than 0.5 parts by mass and not more than 3 parts by mass, more preferably not less than 0.5 parts by mass and not more than 2.5 parts by mass, relative to 100 parts by mass of the conductive powder.

又,氧化錳粉末之數平均粒徑較好為0.8μm以下,基於抑制於厚膜導體表面浮出玻璃之現象的觀點,更好設為0.2μm以上0.8μm以下。數平均粒徑大於0.8μm時,導電粉末或無鉛玻璃粉末無法均質分散,有氧化錳粉末偏置之虞。又,雖亦可使用數平均粒徑未達0.2μm者,但一般可容易獲得0.2μm以上的粉末。此處,數平均粒徑係自粉末之掃描顯微鏡照片(SEM像)求出之數平均粒徑。Also, the number average particle diameter of the manganese oxide powder is preferably at most 0.8 μm, more preferably at least 0.2 μm and at most 0.8 μm from the viewpoint of suppressing the phenomenon of glass floating on the surface of the thick-film conductor. When the number average particle diameter exceeds 0.8 μm, the conductive powder or the lead-free glass powder cannot be dispersed homogeneously, and the manganese oxide powder may be biased. Also, those having a number average particle diameter of less than 0.2 μm can also be used, but generally, powders of 0.2 μm or more can be easily obtained. Here, the number average particle diameter is the number average particle diameter calculated|required from the scanning micrograph (SEM image) of a powder.

又,作為氧化錳可使用MnO2 (二氧化錳)或Mn3 O4 (四氧化三錳)等,例如藉由使用Mn3 O4 (四氧化三錳),可於厚膜導體表面形成微細階差狀之條紋花樣,發揮錨定效果。In addition, MnO 2 (manganese dioxide) or Mn 3 O 4 (trimanganese tetraoxide) can be used as manganese oxide. For example, by using Mn 3 O 4 (trimanganese tetraoxide), fine Step-like striped pattern exerts an anchoring effect.

(氧化物粉末)   厚膜導體形成用粉末組成物除了上述無鉛玻璃粉末或氧化錳粉末以外,在不阻礙本發明效果之範圍可含有該等以外之氧化物粉末。例如,基於提高厚膜導體之接著強度、耐酸性、焊料濡濕性等之目的,可添加至少一種以上之Bi2 O3 、SiO2 、CuO、ZnO、TiO2 、ZrO2 、MnO2 等之氧化物粉末。惟,基於抑制電阻值上升之觀點,無鉛玻璃粉末及氧化錳粉末以外之氧化物粉末的含量,相對於導電粉末100質量份,該等之合計較好侷限於0~10質量份左右之範圍內。(Oxide Powder) The powder composition for forming a thick-film conductor may contain other oxide powders in addition to the above-mentioned lead-free glass powder or manganese oxide powder within the range that does not inhibit the effect of the present invention. For example, based on the purpose of improving the bonding strength, acid resistance, solder wettability, etc. of thick film conductors, at least one oxide of Bi 2 O 3 , SiO 2 , CuO, ZnO, TiO 2 , ZrO 2 , MnO 2 , etc. can be added. material powder. However, from the viewpoint of suppressing the increase in resistance value, the content of oxide powders other than lead-free glass powder and manganese oxide powder is preferably limited to a range of about 0 to 10 parts by mass relative to 100 parts by mass of conductive powder. .

又,本發明之厚膜導體形成用粉末組成物較好為導電粉末、無鉛玻璃粉末及氧化錳混合而成之混合物。藉由為混合物,可獲得內容物更均一的厚膜導體形成用糊料或厚膜導體。作為混合方法,可使用球磨機、珠磨機等之習知技術,藉由該等技術,可獲得充分均一之混合物。Furthermore, the powder composition for forming a thick-film conductor of the present invention is preferably a mixture of conductive powder, lead-free glass powder, and manganese oxide. By being a mixture, a thick-film conductor-forming paste or a thick-film conductor having a more uniform content can be obtained. As a mixing method, known techniques such as a ball mill and a bead mill can be used, and a sufficiently uniform mixture can be obtained by these techniques.

[(2)厚膜導體形成用糊料]   本發明之厚膜導體形成用糊料之一例係包含上述之厚膜導體形成用粉末組成物、溶劑與樹脂之混合物的糊料。[(2) Paste for forming thick-film conductors] An example of the paste for forming thick-film conductors of the present invention is a paste comprising a mixture of the above-mentioned powder composition for forming thick-film conductors, a solvent, and a resin.

作為溶劑,可使用糊料中一般使用之松油醇或丁基卡必醇等,關於樹脂,亦可使用糊料中一般使用之乙基纖維素或甲基丙烯酸酯等。樹脂與溶劑係預先混合作成有機載劑之狀態,使用其可製造厚膜導體形成用糊料。例如基於成本及處理之容易性之觀點,可將乙基纖維素溶解於松油醇者作成有機載劑。有機載劑中,樹脂與溶劑之比例係對應於最終厚膜導體形成用糊料組成的印刷性或塗佈方法而適當選擇。As a solvent, terpineol, butyl carbitol, etc. which are generally used in pastes can be used, and as a resin, ethyl cellulose, methacrylate, etc. which are generally used in pastes can also be used. Resin and solvent are pre-mixed to form an organic vehicle, which can be used to produce a thick-film conductor-forming paste. For example, from the viewpoint of cost and ease of handling, ethyl cellulose can be dissolved in terpineol as an organic vehicle. In the organic vehicle, the ratio of the resin to the solvent is appropriately selected according to the printability or the coating method of the final thick-film conductor-forming paste composition.

作為有機載劑之於厚膜導體形成用糊料中之含量,相對於前述導電粉末100質量份,可為15質量份以上250質量份以下。有機載劑之含量未達15質量份時,有黏度過高而實質上無法塗佈之情況,且,該含量超過250質量份時,有產生粒子沉降或燒成後之厚膜導體之膜緻密性大為降低的問題之虞。考慮印刷性或塗佈容易性、作為糊料之粒子沉降或厚膜導體之膜的緻密性時,該含量較好設為20質量份以上100質量份以下。The content of the organic vehicle in the paste for forming a thick-film conductor may be 15 parts by mass or more and 250 parts by mass or less with respect to 100 parts by mass of the aforementioned conductive powder. When the content of the organic vehicle is less than 15 parts by mass, the viscosity may be too high to be applied substantially, and when the content exceeds 250 parts by mass, particle sedimentation may occur or the film of the thick-film conductor after firing may become dense. The risk of the problem of greatly reduced sex. The content is preferably at least 20 parts by mass and not more than 100 parts by mass in consideration of printability, easiness of coating, sedimentation of particles as a paste, or denseness of a film of a thick-film conductor.

本發明之厚膜導體形成用糊料可藉由混練厚膜導體形成用粉末組成物與有機載劑而製造。作為混練方法並未特別限定,但可使用例如濕式混練磨機、輥磨機、輥柱磨機等之習知技術進行混練。又,所得導體糊料之黏度係根據目的之厚膜導體的膜厚或陶瓷基板種類等而適當選擇。The thick-film conductor-forming paste of the present invention can be produced by kneading the thick-film conductor-forming powder composition and an organic vehicle. The kneading method is not particularly limited, but kneading can be performed using known techniques such as wet kneading mill, roll mill, and roll mill. In addition, the viscosity of the obtained conductor paste is suitably selected according to the film thickness of the intended thick-film conductor, the kind of ceramic substrate, etc.

又,作為本發明之厚膜導體形成用糊料之上述以外之例,舉例為下述厚膜導體形成用糊料,其包含導電粒子、無鉛玻璃粒子、氧化錳粒子、溶劑及樹脂,前述玻璃粒子之含量,相對於前述導電粒子100質量份,為1.5質量份以上5質量份以下,前述氧化錳粒子含量,相對於前述導電粒子100質量份,為0.5質量份以上3.5質量份以下。In addition, examples of the thick-film conductor-forming paste of the present invention other than those described above include the following thick-film conductor-forming paste, which contains conductive particles, lead-free glass particles, manganese oxide particles, a solvent, and a resin. The particle content is 1.5 to 5 parts by mass relative to 100 parts by mass of the conductive particles, and the manganese oxide particle content is 0.5 to 3.5 parts by mass based on 100 parts by mass of the conductive particles.

關於導電粒子、無鉛玻璃粒子、氧化錳粒子、無鉛玻璃粒子含量及氧化錳粒子含量,係如上述厚膜導體形成用粉末組成物脂項目中所說明,於此處省略說明。又,關於溶劑及樹脂,由於亦如上述厚膜導體形成用糊料之一例中所說明,故省略說明。The conductive particles, the lead-free glass particles, the manganese oxide particles, the content of the lead-free glass particles, and the manganese oxide particle content are as described in the item of the above-mentioned powder composition resin for forming thick film conductors, and the description is omitted here. Also, the solvent and the resin are as described in the above-mentioned example of the paste for forming a thick-film conductor, so the description is omitted.

本發明之厚膜導體形成用糊料可藉由於例如有機載劑中分別添加導電粒子、無鉛玻璃粒子、氧化錳粒子作成混合物,混練該混合物而製造。作為混練方法並未特別限定,但可使用例如濕式混練磨機、輥磨機、輥柱磨機等之習知技術進行混練。又,所得導體糊料之黏度係根據目的之厚膜導體的膜厚或陶瓷基板種類等而適當選擇。The thick-film conductor-forming paste of the present invention can be produced by adding conductive particles, lead-free glass particles, and manganese oxide particles to an organic vehicle to form a mixture, and kneading the mixture. The kneading method is not particularly limited, but kneading can be performed using known techniques such as wet kneading mill, roll mill, and roll mill. In addition, the viscosity of the obtained conductor paste is suitably selected according to the film thickness of the intended thick-film conductor, the kind of ceramic substrate, etc.

又,上述說明之厚膜導體形成用糊料中,除了上述無鉛玻璃粉末或氧化錳粉末以外,在不阻礙本發明效果之範圍可含有該等以外之氧化物粉末。例如,基於提高厚膜導體之接著強度、耐酸性、焊料濡濕性等之目的,可添加至少一種以上之Bi2 O3 、SiO2 、CuO、ZnO、TiO2 、ZrO2 、MnO2 等之氧化物粉末。惟,基於抑制電阻值上升之觀點,無鉛玻璃粉末及氧化錳粉末以外之氧化物粉末的含量,相對於導電粉末100質量份,該等之合計較好侷限於0~10質量份左右之範圍內。In addition, the paste for forming a thick-film conductor described above may contain oxide powders other than the above-mentioned lead-free glass powder or manganese oxide powder within the range that does not inhibit the effect of the present invention. For example, based on the purpose of improving the bonding strength, acid resistance, solder wettability, etc. of thick film conductors, at least one oxide of Bi 2 O 3 , SiO 2 , CuO, ZnO, TiO 2 , ZrO 2 , MnO 2 , etc. can be added. material powder. However, from the viewpoint of suppressing the increase in resistance value, the content of oxide powders other than lead-free glass powder and manganese oxide powder is preferably limited to a range of about 0 to 10 parts by mass relative to 100 parts by mass of conductive powder. .

[(3)厚膜導體之製造方法]   厚膜導體之製造方法可包含將例如本發明之厚膜導體形成用糊料塗佈於陶瓷基板之塗佈步驟,將塗佈有前述糊料之基板乾燥之乾燥步驟,及隨後於500℃以上且未達900℃之溫度下燒成之燒成步驟。[(3) Method for producing thick-film conductor] The method for producing a thick-film conductor may include a step of applying, for example, the thick-film conductor-forming paste of the present invention to a ceramic substrate, and the substrate coated with the aforementioned paste A drying step of drying, and a subsequent firing step of firing at a temperature of 500°C or higher and less than 900°C.

(塗佈步驟)   又,作為塗佈方法並未特別限定,可使用網版印刷、凸版印刷或凹版印刷等之印刷法,此外可使用利用佈膠器之描繪方式等之習知技術,但基於適當膜厚且進行大量生產之觀點,較好藉由網版印刷法塗佈。作為陶瓷基板,係對應於電子零件之用途,使用96%氧化鋁基板、鎂橄欖石等,但本發明之厚膜導體形成用糊料可適用於任何基板。(Coating step) Also, the coating method is not particularly limited, and printing methods such as screen printing, letterpress printing, or gravure printing can be used, and conventional techniques such as drawing methods using a glue dispenser can be used, but based on From the viewpoint of appropriate film thickness and mass production, it is preferable to apply by screen printing method. As ceramic substrates, 96% alumina substrates, forsterite, etc. are used for electronic parts, but the thick-film conductor-forming paste of the present invention can be applied to any substrates.

(乾燥步驟)   塗佈厚膜導體形成用糊料後,將塗佈後之膜連同陶瓷基板一起於80℃以上200℃以下之溫度條件下,乾燥2分鐘以上15分鐘以下之時間。如此,藉由於塗佈步驟與燒成步驟之間設置乾燥步驟,由於可防止燒成時因溶劑等之揮發成分殘存所致之溶劑等之揮發及燃燒,故於燒成步驟中使用燒成爐時等,可獲得防止燒成爐汙染之效果。該步驟中,乾燥方法並未特別限制,可使用烘箱或輸送式乾燥爐等之習知手段,但基於量產性之觀點,較好為利用輸送式乾燥爐之乾燥。又,乾燥溫度未達80℃時,乾燥所需之時間變長,故有生產性惡化而欠佳之情況。又,乾燥溫度超過200℃時,由於有樹脂氧化而乾燥後之膜變脆之情況,故而欠佳。(Drying step) After coating the thick-film conductor-forming paste, dry the coated film together with the ceramic substrate at a temperature of 80°C to 200°C for 2 minutes to 15 minutes. In this way, by providing a drying step between the coating step and the firing step, volatilization and burning of solvents and the like due to the remaining volatile components of the solvent and the like during firing can be prevented, so the firing furnace is used in the firing step Time, etc., can obtain the effect of preventing the pollution of the firing furnace. In this step, the drying method is not particularly limited, and conventional means such as an oven or a conveyor drying oven can be used, but from the viewpoint of mass productivity, drying using a conveyor drying oven is preferred. Moreover, when drying temperature is less than 80 degreeC, since the time required for drying becomes long, productivity may deteriorate and it may be unfavorable. Also, when the drying temperature exceeds 200° C., the film after drying may become brittle due to oxidation of the resin, which is not preferable.

(燒成步驟)   乾燥步驟後之燒成步驟中,將乾燥後之膜與陶瓷基板一起加熱燒成膜。作為燒成方法較好使用輸送爐。該情況下,燒成中之峰值溫度為500℃以上且未達900℃,較好為700℃以上且未達900℃。峰值溫度未達500℃時,玻璃粉末之熔融未充分進行,有阻礙與陶瓷基板的密著性的問題之虞。另一方面,峰值溫度為900℃以上時,有膜過度燒結之虞,尤其是使用以熔點低的Ag作為主成分之厚膜導體形成用糊料時,導電粒子與玻璃粒子等會分離而使厚膜導體形成為島狀,有產生無法形成均一電極膜的問題之虞。(Firing step) In the firing step following the drying step, the dried film is heated together with the ceramic substrate to form a film. As a firing method, it is preferable to use a conveyor furnace. In this case, the peak temperature during firing is not less than 500°C and not more than 900°C, preferably not less than 700°C and not more than 900°C. When the peak temperature is less than 500° C., melting of the glass powder does not proceed sufficiently, and there may be a problem that the adhesion with the ceramic substrate is inhibited. On the other hand, when the peak temperature is 900°C or higher, there is a possibility of excessive sintering of the film. In particular, when using a paste for forming a thick-film conductor whose main component is Ag with a low melting point, the conductive particles and glass particles are separated and the The thick-film conductor is formed in an island shape, which may cause a problem that a uniform electrode film cannot be formed.

於上述峰值溫度,必須保持5分鐘以上20分鐘以下,較好7分鐘以上13分鐘以下。峰值溫度之保持時間超過20分鐘時,有厚膜導體膜變過度燒結之可能性,該保持時間未達5分鐘時,有燒結不充分之虞。且,升溫至峰值溫度、峰值溫度之保持及自峰值溫度之冷卻之燒成步驟中的總時間必須為20分鐘以上90分鐘以下,較好為30分鐘以上60分鐘以下。總時間未達20分鐘時,升溫速度及冷卻速度過大,有因急遽溫度變化而於厚膜導體發生龜裂之虞。又,總時間超過90分鐘時,有產生生產性惡化的問題之虞。At the above-mentioned peak temperature, it must be maintained for 5 minutes to 20 minutes, preferably 7 minutes to 13 minutes. When the holding time of the peak temperature exceeds 20 minutes, there is a possibility that the thick conductor film becomes excessively sintered, and when the holding time is less than 5 minutes, there is a possibility that the sintering is insufficient. In addition, the total time in the firing steps of raising the temperature to the peak temperature, maintaining the peak temperature, and cooling from the peak temperature must be 20 minutes to 90 minutes, preferably 30 minutes to 60 minutes. When the total time is less than 20 minutes, the heating rate and the cooling rate are too high, and there is a possibility that cracks may occur in the thick-film conductor due to a rapid temperature change. Moreover, when the total time exceeds 90 minutes, there exists a possibility that the problem of deterioration of productivity may arise.

為了以上述峰值溫度及燒成時間進行燒成,直至峰值溫度之升溫速度較好設為20℃/分鐘以上150℃/分鐘以下,自峰值溫度之冷卻速度設為20℃/分鐘以上200℃/分鐘。升溫速度未達20℃/分鐘或冷卻速度未達20℃/分鐘時,由於有生產性惡化之虞故而欠佳。且,升溫速度超過150℃/分鐘或冷卻速度超過200℃/分鐘時,由於有因急遽溫度變化而於厚膜導體產生龜裂之可能性之虞,故而欠佳。In order to perform firing at the above-mentioned peak temperature and firing time, the heating rate up to the peak temperature is preferably 20°C/min to 150°C/min, and the cooling rate from the peak temperature is preferably 20°C/min to 200°C/min. minute. When the rate of temperature rise is less than 20° C./minute or the rate of cooling is less than 20° C./minute, it is unfavorable because productivity may deteriorate. Furthermore, when the heating rate exceeds 150° C./minute or the cooling rate exceeds 200° C./minute, cracks may occur in the thick-film conductor due to a sudden temperature change, which is not preferable.

又,燒成中之環境並未特別限定,但基於無鉛玻璃的軟化點之觀點,較好於空氣環境中燒成。Also, the environment during firing is not particularly limited, but firing in an air environment is preferable from the viewpoint of the softening point of lead-free glass.

[(4)厚膜導體]   藉由上述製造方法,自本發明之厚膜導體形成用糊料所得之厚膜導體包含導電成分、因玻璃粉末熔融所得之玻璃成分與氧化錳。氧化錳意指熔入玻璃中之狀態。[(4) Thick-film conductor] The thick-film conductor obtained from the thick-film conductor-forming paste of the present invention by the above-mentioned production method contains a conductive component, a glass component obtained by fusing glass powder, and manganese oxide. Manganese oxide refers to the state of melting into glass.

而且該厚膜導體因包含氧化錳,而使玻璃浮出於表面較少,且於表面產生微細階差狀之條紋花樣。Moreover, since the thick-film conductor contains manganese oxide, less glass floats to the surface, and fine-stepped stripe patterns are produced on the surface.

厚膜導體之期望膜厚為5.0μm以上10.0μm以下。若為該膜厚範圍,則滿足厚膜導體對陶瓷基板之密著性,並且可抑制玻璃朝厚膜導體表面之浮出。The desired film thickness of the thick film conductor is not less than 5.0 μm and not more than 10.0 μm. Within this film thickness range, the adhesion of the thick-film conductor to the ceramic substrate is satisfied, and the floating of glass to the surface of the thick-film conductor can be suppressed.

因此,使用本發明之厚膜導體形成用糊料製造之厚膜導體與陶瓷基板之接著強度亦良好,可謂滿足良好之鍍敷附著性,成為具備鍍敷優異之特性者。良好鍍敷附著性可以Ni電鍍之膜厚予以評價。以相同電流密度實施Ni電鍍時,確認到於表面局部有浮出玻璃之厚膜導體,其鍍敷膜厚亦薄於添加氧化錳而抑制表面玻璃浮起之厚膜導體。 [實施例]Therefore, the thick-film conductor manufactured using the thick-film conductor-forming paste of the present invention also has good bonding strength to the ceramic substrate, which can be said to satisfy good plating adhesion and have excellent characteristics of plating. Good plating adhesion can be evaluated by the film thickness of Ni plating. When Ni electroplating was performed at the same current density, it was confirmed that there was a thick-film conductor with glass floating on the surface locally, and the thickness of the plating film was also thinner than that of a thick-film conductor that suppressed glass floating on the surface by adding manganese oxide. [Example]

以下,針對本發明,利用實施例進一步進行說明,但本發明之範圍並非受該實施例之限制。Hereinafter, the present invention will be further described using examples, but the scope of the present invention is not limited by the examples.

實施例1~7及比較例1~3中,使用以下所示之導電粉末及氧化錳粉末及表1所示之球狀無鉛玻璃粉末1、2之任一者,製作厚膜導體形成用粉末組成物及厚膜導體形成用糊料,進而製造厚膜導體。針對所得厚膜導體,進行燒成膜厚之測定、表面狀態之觀察、電阻值之測定及與基板之接著強度之評價。又,表1中之鹼金屬氧化物的總計主要為Li、K及Na之金屬氧化物之總計。In Examples 1 to 7 and Comparative Examples 1 to 3, the conductive powder and manganese oxide powder shown below and any of the spherical lead-free glass powders 1 and 2 shown in Table 1 were used to produce thick film conductor forming powder Composition and paste for forming thick film conductors, and further manufacture thick film conductors. For the obtained thick-film conductor, the measurement of the fired film thickness, the observation of the surface state, the measurement of the resistance value, and the evaluation of the bonding strength with the substrate were carried out. Also, the total of alkali metal oxides in Table 1 is mainly the total of metal oxides of Li, K, and Na.

Figure 02_image001
Figure 02_image001

(導電粉末)   作為導電粉末係使用銀粉末或銀與鈀之合金粉末。銀粉末A為數平均粒徑為2.0μm之粉末,銀粉末B為數平均粒徑為5.0μm之粉末。又,鈀粉末之數平均粒徑為0.2μm。(Conductive powder) As the conductive powder, silver powder or alloy powder of silver and palladium is used. The silver powder A is a powder having a number average particle diameter of 2.0 μm, and the silver powder B is a powder having a number average particle diameter of 5.0 μm. In addition, the number average particle diameter of the palladium powder was 0.2 μm.

(氧化錳粉末)   作為氧化錳粉末係使用Mn3 O4 (數平均粒徑為0.5μm)。(Manganese oxide powder) Mn 3 O 4 (number average particle diameter: 0.5 μm) was used as the manganese oxide powder.

[厚膜導體形成用粉末組成物之製作]   將導電粉末、無鉛玻璃粉末及氧化錳粉末以如表2所示組成予以混合,藉由球磨機攪拌,製作厚膜導體形成用粉末組成物。[Preparation of thick-film conductor-forming powder composition] Conductive powder, lead-free glass powder, and manganese oxide powder were mixed with the composition shown in Table 2, and stirred by a ball mill to prepare a thick-film conductor-forming powder composition.

[厚膜導體形成用糊料之製作]   將上述製作之厚膜導體形成用粉末組成物72.5質量%與有機載劑27.5質量%混合,隨後藉由3輥研磨機混練,製作厚膜導體形成用糊料。又,有機載劑係將乙基纖維素7質量%與溶劑的松油醇溶液93質量%混合並加熱使乙基纖維素溶解而製作。[Preparation of Paste for Forming Thick Film Conductor] Mix 72.5% by mass of the powder composition for forming thick film conductor prepared above with 27.5% by mass of organic vehicle, and then knead with a 3-roll mill to prepare thick film conductor. paste. In addition, the organic vehicle was prepared by mixing 7% by mass of ethyl cellulose and 93% by mass of a terpineol solution as a solvent, followed by heating to dissolve the ethyl cellulose.

[厚膜導體之製作]   將上述製作之厚膜導體形成用糊料藉由網版印刷機網版印刷於96%氧化鋁基板(25.4mm×25.4mm×1mm)上(塗佈步驟),使用輸送式乾燥爐於150℃乾燥5分鐘(乾燥步驟)。經乾燥之膜及氧化鋁基板於峰值溫度850℃燒成9分鐘以總計30分鐘之輸送爐燒成(燒成步驟),形成特定圖型之厚膜導體。[Manufacturing of thick film conductors] The paste for forming thick film conductors prepared above was screen-printed on a 96% alumina substrate (25.4mm×25.4mm×1mm) by a screen printing machine (coating step), and used Dry in a conveyor drying oven at 150° C. for 5 minutes (drying step). The dried film and alumina substrate were fired at a peak temperature of 850°C for 9 minutes and then fired in a conveyor furnace for a total of 30 minutes (firing step) to form a thick film conductor with a specific pattern.

[厚膜導體之物性評價]   針對上述製造之厚膜導體,藉由以下所示方法,進行燒成膜厚之測定、表面狀態之觀察、電阻值之測定、與氧化鋁基板之接著強度及鎳鍍敷之鍍敷膜厚的評價。評價結果示於表2。[Evaluation of physical properties of thick-film conductors] For the thick-film conductors produced above, measurement of fired film thickness, observation of surface state, measurement of resistance value, adhesion strength with alumina substrate and nickel were carried out by the following methods. Evaluation of plating film thickness. The evaluation results are shown in Table 2.

(燒成膜厚之測定)   針對燒成後之厚膜導體膜厚,使用接觸式表面粗糙度計以n=5進行測定。(Measurement of Firing Film Thickness) The film thickness of the thick film conductor after firing was measured with n=5 using a contact surface roughness meter.

(鍍敷膜厚)   對燒成後之厚膜導體實施Ni電鍍之樣品,使用接觸式表面粗糙度計以n=5測定自氧化鋁基板至Ni電鍍面之厚度,自所得結果導出厚膜導體之膜厚算出鍍敷膜厚。(Plating Film Thickness) The thickness of the Ni-plated thick-film conductor was measured using a contact surface roughness meter with n=5, and the thickness of the thick-film conductor was derived from the obtained results. Calculate the thickness of the coating film.

(表面狀態之觀察)   針對厚膜導體表面狀態,使用SEM(掃描型電子顯微鏡)予以觀察,確認階差狀條紋花樣之有無及玻璃浮出之有無。且,圖2顯示實施例1之厚膜導體的SEM圖像,圖3顯示比較例1之厚膜導體的SEM圖像。(Observation of surface state) The surface state of the thick film conductor was observed using a SEM (scanning electron microscope) to confirm the presence or absence of step-like stripe patterns and the presence or absence of glass floating. 2 shows the SEM image of the thick film conductor of Example 1, and FIG. 3 shows the SEM image of the thick film conductor of Comparative Example 1.

(電阻值測定)   針對於氧化鋁基板上以寬0.5mm、長50mm之圖型形成之厚膜導體的樣品,藉由數位萬用表測定其電阻值。(Measurement of resistance value) The resistance value of a sample of a thick film conductor formed on an alumina substrate in a pattern of 0.5 mm in width and 50 mm in length was measured by a digital multimeter.

(接著強度之評價)   對於氧化鋁基板上以2.0mm×2.0mm之墊片狀圖型作成之厚膜導體,作為Ni鍍敷液係使用調製為硫酸鎳係280g/L、氯化鎳係60g/L、硼酸係40g/L的鍍敷液,將電流密度設為5×10-3 A/mm2 (5×10-9 A/m2 ),實施2分鐘之Ni電鍍,作為樣品。對實施該鍍敷之樣品,使用96.5質量% Sn-3質量%Ag-0.5質量%Cu組成之無鉛焊料,施以直徑0.65mm之Sn鍍敷銅線之焊接者作為試驗片。藉由拉伸試驗機,將試驗片之Sn鍍敷銅線於氧化鋁基板之垂直方向拉伸,將厚膜導體膜自氧化鋁基板剝離,測定該剝離時之拉伸力,算出最大值、最小值及平均值而評價接著強度之初期強度。且,對於與上述試驗片同樣者,施加150℃24小時之熱負載而劣化後,進行同樣拉伸試驗,算出最大值、最小值及平均值而評價熱劣化接著強度。初期接著強度及熱劣化接著強度均評價15片試驗片。(Evaluation of Adhesion Strength) For a thick-film conductor formed on an alumina substrate with a spacer pattern of 2.0mm×2.0mm, as a Ni plating solution, 280g/L of nickel sulfate and 60g of nickel chloride were used. /L, 40 g/L boric acid-based plating solution, set the current density to 5×10 -3 A/mm 2 (5×10 -9 A/m 2 ), perform Ni electroplating for 2 minutes, and make a sample. For the samples subjected to this plating, a lead-free solder composed of 96.5% by mass Sn-3% by mass of Ag-0.5% by mass of Cu was used as a test piece which was welded with a Sn-plated copper wire with a diameter of 0.65 mm. Using a tensile testing machine, the Sn-plated copper wire of the test piece was stretched in the vertical direction of the alumina substrate, and the thick film conductor film was peeled off from the alumina substrate, and the tensile force at the time of peeling was measured, and the maximum value, The minimum and average values are used to evaluate the initial strength of the bonding strength. Then, the same test piece as above was subjected to a thermal load at 150° C. for 24 hours to cause deterioration, and then the same tensile test was performed to calculate the maximum value, minimum value, and average value to evaluate thermally deteriorated adhesive strength. 15 test pieces were evaluated for both the initial bonding strength and the thermally deteriorated bonding strength.

Figure 02_image003
Figure 02_image003

(關於厚膜導體之膜厚及電阻值)   厚膜導體之膜厚於實施例1~7及比較例1~3之任一者均為5.0μm以上10.0μm以下之範圍內,未見到膜厚異常。且,關於電阻值,使用銀作為導電粉末或使用銀與鈀作為導電粉末所得之值雖見到不同,但該等值並無異常,且實施例1~7及比較例1~3之任一者均為無問題之值。(About the film thickness and resistance value of the thick film conductor) The film thickness of the thick film conductor is within the range of 5.0 μm to 10.0 μm in any of Examples 1 to 7 and Comparative Examples 1 to 3, and no film is seen. Abnormally thick. And, regarding the resistance value, although the values obtained by using silver as the conductive powder or using silver and palladium as the conductive powder are different, there is no abnormality in the equivalent values, and any of Examples 1-7 and Comparative Examples 1-3 Both are non-problematic values.

(接著強度之評價)   由實施例1~7之評價結果,接著強度於初期評價及熱劣化後之評價其值均無問題。又,藉由使用包含鉍之玻璃粉末,於初期及熱劣化後之任一者,均見到接著強度提高之效果(實施例5、6)。(Evaluation of Adhesive Strength) From the evaluation results of Examples 1 to 7, there is no problem with the initial evaluation and evaluation of the adhesive strength after thermal deterioration. Also, by using glass powder containing bismuth, the effect of improving the adhesion strength was observed both at the initial stage and after thermal deterioration (Examples 5 and 6).

又,由實施例1~3與比較例1之結果,於初期及熱劣化後之任一者均確認到藉由含有錳而接著強度提高之效果。該效果於併用銀與鈀作為導電粉末時顯著見到(實施例4、比較例2),尤其為對熱劣化後之接著強度有較大影響之結果。Also, from the results of Examples 1 to 3 and Comparative Example 1, the effect of improving the adhesive strength by containing manganese was confirmed both at the initial stage and after thermal deterioration. This effect is remarkably seen when silver and palladium are used together as the conductive powder (Example 4, Comparative Example 2), especially because it has a great influence on the adhesive strength after thermal deterioration.

又,因含有錳而對接著強度之效果,確認到若相對於導電粉末100質量份含有0.3質量份則可發揮(比較例3)。Moreover, it was confirmed that the effect of containing manganese on the adhesive strength can be exhibited when 0.3 parts by mass is contained with respect to 100 parts by mass of the conductive powder (comparative example 3).

(表面狀態之觀察結果)   實施例1~7中,確認到因含有錳所致之階差狀條紋花樣,係因錨定效果而可期待鍍敷附著性提高之表面狀態。比較例1、2中,未含有錳,未見到條紋花樣。且,比較例3中,雖大致見到因含有錳所致之條紋花樣,但並無可期待錨定效果程度之階差狀花樣。(Observation results of surface state) In Examples 1 to 7, it was confirmed that the step-like stripe pattern due to the inclusion of manganese is a surface state in which plating adhesion can be expected to be improved due to the anchoring effect. In Comparative Examples 1 and 2, no manganese was contained, and no stripe pattern was observed. In addition, in Comparative Example 3, although a striped pattern due to the manganese content was generally observed, there was no stepped pattern to the extent that an anchoring effect can be expected.

又,針對玻璃浮出之有無,於實施例1~7中,因含有錳而未見到玻璃之浮起,可知係可抑制銀硫化者。又,比較例3中,由於見到玻璃浮起,故可知錳含量不足。且,比較例1、2中,因不含錳而見到玻璃浮起,成為提示即使施以Ni鍍敷亦有發生銀的硫化現象之虞的結果。Also, regarding the presence or absence of glass floating, in Examples 1 to 7, glass floating was not observed because manganese was contained, and it was found that silver sulfide was suppressed. Moreover, in the comparative example 3, since glass floating was seen, it turned out that manganese content was insufficient. In addition, in Comparative Examples 1 and 2, since manganese was not contained, glass floating was observed, which was a result suggesting that silver sulfide phenomenon might occur even if Ni plating was applied.

(鍍敷膜厚)   比較實施例2與7、比較例1之Ni電鍍膜厚時,可知含有氧化錳之實施例2、7比不含氧化錳之比較例1更厚。且,亦可明瞭由添加氧化錳之厚膜導體形成用粉末組成物所得之厚膜導體之鍍敷附著性比不含氧化錳者更優異。(Plating film thickness) When comparing the Ni plating film thickness of Examples 2 and 7, and Comparative Example 1, it can be seen that Examples 2 and 7 containing manganese oxide are thicker than Comparative Example 1 not containing manganese oxide. Furthermore, it was also found that the thick-film conductor obtained from the powder composition for forming a thick-film conductor to which manganese oxide was added had better plating adhesion than that containing no manganese oxide.

[總結]   如由實施例所了解,可知依據本發明之厚膜導體形成用粉末組成物及厚膜導體形成用糊料之製造方法,可提供容易施以鍍敷且抑制銀硫化之厚膜導體。[Summary] As understood from the examples, it can be seen that the powder composition for forming a thick film conductor and the method for producing a paste for forming a thick film conductor according to the present invention can provide a thick film conductor that is easy to be plated and suppresses silver sulfide .

以上,針對本發明之較佳實施形態詳細說明,但本發明不限定於該等例。若為本發明所屬技術領域中具有通常知識者,可明瞭在申請專利範圍所記載之技術思想範圍內,可想到各種變化例或修正例,針對該等,應了解當然屬於本發明之技術範圍。As mentioned above, although the preferred embodiment of this invention was demonstrated in detail, this invention is not limited to these examples. Those who have ordinary knowledge in the technical field to which the present invention pertains can understand that various variations or amendments can be conceived within the scope of the technical ideas described in the scope of the patent application, and it should be understood that these naturally belong to the technical scope of the present invention.

10‧‧‧氧化鋁基板20‧‧‧內部電極21‧‧‧上面電極22‧‧‧側面電極23‧‧‧背面電極30‧‧‧電阻膜40‧‧‧保護膜50‧‧‧中間電極60‧‧‧外部電極100‧‧‧晶片電阻器10‧‧‧alumina substrate 20‧‧‧internal electrode 21‧‧‧top electrode 22‧‧‧side electrode 23‧‧‧back electrode 30‧‧‧resistive film 40‧‧‧protective film 50‧‧‧middle electrode 60 ‧‧‧External electrode 100‧‧‧chip resistor

圖1係晶片電阻器之剖面示意圖。   圖2係顯示實施例1之厚膜導體的SEM圖像的圖。   圖3係顯示比較例1之厚膜導體的SEM圖像的圖。Figure 1 is a schematic cross-sectional view of a chip resistor. Figure 2 is a diagram showing the SEM image of the thick film conductor of Example 1. Fig. 3 is a diagram showing the SEM image of the thick film conductor of Comparative Example 1.

10‧‧‧氧化鋁基板 10‧‧‧Alumina substrate

20‧‧‧內部電極 20‧‧‧internal electrodes

21‧‧‧上面電極 21‧‧‧top electrode

22‧‧‧側面電極 22‧‧‧Side electrode

23‧‧‧背面電極 23‧‧‧Rear electrode

30‧‧‧電阻膜 30‧‧‧resistive film

40‧‧‧保護膜 40‧‧‧Protective film

50‧‧‧中間電極 50‧‧‧intermediate electrode

60‧‧‧外部電極 60‧‧‧External electrodes

100‧‧‧晶片電阻器 100‧‧‧chip resistor

Claims (9)

一種厚膜導體形成用粉末組成物,作為粉末,其僅包含導電粉末、無鉛玻璃粉末、及氧化錳粉末,前述無鉛玻璃粉末含量,相對於前述導電粉末100質量份,為1.5質量份以上5質量份以下,前述氧化錳粉末含量,相對於前述導電粉末100質量份,為0.5質量份以上3.5質量份以下,前述氧化錳粉末之數平均粒徑為0.8μm以下。 A powder composition for forming a thick-film conductor, the powder comprising only conductive powder, lead-free glass powder, and manganese oxide powder, wherein the content of the lead-free glass powder is 1.5 parts by mass or more than 5 parts by mass relative to 100 parts by mass of the conductive powder The content of the manganese oxide powder is not less than 0.5 parts by mass and not more than 3.5 parts by mass relative to 100 parts by mass of the conductive powder, and the number average particle diameter of the manganese oxide powder is not more than 0.8 μm. 一種厚膜導體形成用粉末組成物,作為粉末,其僅包含導電粉末、無鉛玻璃粉末、氧化錳粉末、氧化物粉末,前述無鉛玻璃粉末含量,相對於前述導電粉末100質量份,為1.5質量份以上5質量份以下,前述氧化錳粉末含量,相對於前述導電粉末100質量份,為0.5質量份以上3.5質量份以下,前述氧化錳粉末之數平均粒徑為0.8μm以下, 前述氧化物粉末為選自Bi2O3、SiO2、CuO、ZnO、TiO2、ZrO2、MnO2中之至少1種以上,前述氧化物粉末含量,相對於前述導電粉末100質量份,為0~10質量份。 A powder composition for forming a thick-film conductor. As a powder, it only includes conductive powder, lead-free glass powder, manganese oxide powder, and oxide powder. The content of the aforementioned lead-free glass powder is 1.5 parts by mass relative to 100 parts by mass of the aforementioned conductive powder. More than 5 parts by mass, the content of the manganese oxide powder is 0.5 to 3.5 parts by mass relative to 100 parts by mass of the conductive powder, the number average particle diameter of the manganese oxide powder is 0.8 μm or less, and the oxide powder is At least one selected from Bi 2 O 3 , SiO 2 , CuO, ZnO, TiO 2 , ZrO 2 , and MnO 2 , the content of the oxide powder is 0 to 10 parts by mass relative to 100 parts by mass of the conductive powder . 如請求項1或2之厚膜導體形成用粉末組成物,其中前述氧化錳粉末為Mn3O4粉末。 The powder composition for forming a thick film conductor according to claim 1 or 2, wherein the manganese oxide powder is Mn 3 O 4 powder. 如請求項1或2之厚膜導體形成用粉末組成物,其中前述導電粉末係選自銀粉末、鈀粉末及鉑粉末中之至少一種。 The powder composition for forming a thick film conductor according to claim 1 or 2, wherein the conductive powder is at least one selected from silver powder, palladium powder and platinum powder. 如請求項1或2之厚膜導體形成用粉末組成物,其中前述無鉛玻璃粉末之玻璃轉移溫度為400℃以上600℃以下,軟化點為500℃以上700℃以下。 The powder composition for forming a thick-film conductor according to Claim 1 or 2, wherein the glass transition temperature of the lead-free glass powder is 400°C to 600°C, and the softening point is 500°C to 700°C. 如請求項1或2之厚膜導體形成用粉末組成物,其中前述無鉛玻璃粉末包含鉍。 The powder composition for forming a thick-film conductor according to claim 1 or 2, wherein the lead-free glass powder contains bismuth. 一種厚膜導體形成用糊料,其包含如請求項1至6中任一項之厚膜導體形成用粉末組成物、溶劑與樹脂之混合物。 A paste for forming a thick-film conductor, comprising a mixture of the powder composition for forming a thick-film conductor according to any one of claims 1 to 6, a solvent, and a resin. 一種厚膜導體形成用糊料,其包含導電粒子、 無鉛玻璃粒子、氧化錳粒子、溶劑、及樹脂,前述無鉛玻璃粒子含量,相對於前述導電粒子100質量份,為1.5質量份以上5質量份以下,前述氧化錳粒子含量,相對於前述導電粒子100質量份,為0.5質量份以上3.5質量份以下,前述氧化錳粉末之數平均粒徑為0.8μm以下,作為粉末,僅包含前述導電粒子、前述無鉛玻璃粒子、前述氧化錳粒子。 A kind of paste for thick film conductor formation, it comprises conductive particle, Lead-free glass particles, manganese oxide particles, solvent, and resin, the content of the aforementioned lead-free glass particles is 1.5 to 5 parts by mass with respect to 100 parts by mass of the aforementioned conductive particles, and the content of the aforementioned manganese oxide particles is relative to 100 parts by mass of the aforementioned conductive particles. Parts by mass are 0.5 to 3.5 parts by mass, the number average particle diameter of the manganese oxide powder is 0.8 μm or less, and the powder contains only the conductive particles, the lead-free glass particles, and the manganese oxide particles. 一種厚膜導體形成用糊料,其包含導電粒子、無鉛玻璃粒子、氧化錳粒子、氧化物粒子、溶劑及樹脂,前述無鉛玻璃粒子含量,相對於前述導電粒子100質量份,為1.5質量份以上5質量份以下,前述氧化錳粒子含量,相對於前述導電粒子100質量份,為0.5質量份以上3.5質量份以下,前述氧化錳粉末之數平均粒徑為0.8μm以下, 作為粉末,僅包含前述導電粒子、前述無鉛玻璃粒子、前述氧化錳粒子、前述氧化物粉末,前述氧化物粉末為選自Bi2O3、SiO2、CuO、ZnO、TiO2、ZrO2、MnO2中之至少1種以上,前述氧化物粉末含量,相對於前述導電粉末100質量份,為0~10質量份。 A thick-film conductor-forming paste comprising conductive particles, lead-free glass particles, manganese oxide particles, oxide particles, a solvent, and a resin, wherein the content of the lead-free glass particles is 1.5 parts by mass or more relative to 100 parts by mass of the conductive particles 5 parts by mass or less, the content of the manganese oxide particles is 0.5 to 3.5 parts by mass with respect to 100 parts by mass of the conductive particles, the number average particle diameter of the manganese oxide powder is 0.8 μm or less, and the powder contains only the aforementioned Conductive particles, the aforementioned lead-free glass particles, the aforementioned manganese oxide particles, the aforementioned oxide powder, the aforementioned oxide powder is at least one selected from Bi2O3 , SiO2 , CuO, ZnO, TiO2 , ZrO2 , MnO2 As mentioned above, the said oxide powder content is 0-10 mass parts with respect to 100 mass parts of said conductive powders.
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